Group 15 Elements: The Nitrogen Family

General Properties

1. Elements and Their Symbols:

 Nitrogen (N)
 Phosphorus (P)
 Arsenic (As)
 Antimony (Sb)
 Bismuth (Bi)

2. Electronic Configuration:

 General configuration: 𝑛𝑠2𝑛𝑝3ns2np3

 Example:
 N: 1𝑠22𝑠22𝑝31s22s22p3
 P: [𝑁𝑒]3𝑠23𝑝3[Ne]3s23p3

3. Atomic and Ionic Radii:

 Increases down the group.

 N < P < As < Sb < Bi

4. Ionization Enthalpy:

 Decreases down the group.

 High ionization energy due to stable half-filled p-orbital.

5. Electronegativity:

 Decreases down the group.

 N > P > As > Sb > Bi

6. Melting and Boiling Points:

 Melting and boiling points increase from N to As and then decrease

from Sb to Bi.
Physical Properties

 Nitrogen: Diatomic gas (N₂), colorless, odorless, and tasteless.

 Phosphorus: Exists in several allotropes; white (most reactive), red, and black.
 Arsenic: Metalloid, exists in yellow and gray forms.
 Antimony: Metalloid, exists in metallic form and amorphous forms.
 Bismuth: Metal, brittle, with a pinkish tint.

Chemical Properties

Oxidation States

 Common oxidation states: -3, +3, +5

 Nitrogen exhibits all oxidation states from -3 to +5.
 Heavier elements tend to exhibit +3 oxidation state due to inert pair effect.

Reactivity with Hydrogen

 Form hydrides of type 𝐸𝐻3EH3 (e.g., NH₃, PH₃, AsH₃, SbH₃, BiH₃)
 Stability: NH₃ > PH₃ > AsH₃ > SbH₃ > BiH₃
 Basicity: NH₃ (strongest base) > PH₃ > AsH₃ > SbH₃ > BiH₃

Reactivity with Oxygen

 Form oxides such as 𝐸2𝑂3E2O3 and 𝐸2𝑂5E2O5

 Stability: 𝑁2𝑂5N2O5 (least stable) to Bi₂O₅ (most stable)
 Acidic nature decreases from N₂O₅ (strongly acidic) to Bi₂O₅ (basic).

Reactivity with Halogens

 Form halides 𝐸𝑋3EX3 and 𝐸𝑋5EX5

 Example:
 𝑁𝐶𝑙3NCl3, 𝑃𝐶𝑙3PCl3, 𝐴𝑠𝐶𝑙3AsCl3
 𝑃𝐶𝑙5PCl5, 𝐴𝑠𝐶𝑙5AsCl5 (Bismuth forms only 𝐵𝑖𝐶𝑙3BiCl3)

Reactivity with Metals

 Form binary compounds like nitrides, phosphides, etc.

Anomalous Behavior of Nitrogen

  Small size, high electronegativity, and absence of d-orbitals lead to:
 Ability to form 𝑝𝜋−𝑝𝜋pπ−pπ multiple bonds (e.g., N₂).
 Non-metallic character.
 Formation of a wide range of oxides with different oxidation states.

Important Compounds

Nitrogen

 Ammonia (NH₃): Prepared by Haber process.

 Nitric Acid (HNO₃): Prepared by Ostwald’s process.
 Oxides of Nitrogen: NO, N₂O, NO₂, N₂O₃, N₂O₄, N₂O₅

Phosphorus

 Phosphine (PH₃): Poisonous gas, weaker base than NH₃.

 Phosphoric Acid (H₃PO₄): Weak triprotic acid.
 Phosphorus Pentachloride (PCl₅) and Phosphorus Trichloride (PCl₃):
Chlorinating agents.

Oxoacids of Phosphorus

1. Orthophosphoric Acid (H₃PO₄)

2. Hypophosphorous Acid (H₃PO₂)
3. Phosphorous Acid (H₃PO₃)

Trends in Stability of Compounds

1. Hydrides: Stability decreases down the group.

2. Oxides: Stability of higher oxidation state decreases down the group.
3. Halides: Pentahalides are more covalent and less stable down the group.

Allotropic Forms

 Phosphorus: White, red, and black.

 Arsenic: Yellow (non-metallic) and gray (metallic).
 Antimony: Exists in metallic and amorphous forms.

Industrial Applications

 Ammonia: Fertilizers, explosives.

  Nitric Acid: Fertilizers, explosives, etching.
 Phosphorus: Matches, fertilizers, detergents.

Summary of Key Points

 Group 15 elements show a transition from non-metallic to metallic character

down the group.
 Nitrogen, being the first element, shows distinct behavior.
 Reactivity and properties can be largely understood by considering the trends
in electronegativity, ionization energy, and the inert pair effect.

Mnemonics for Group 15 Elements

 No Problems As Sbi Big (N, P, As, Sb, Bi).